MXPA02002352A - Method for fighting soil insects with phenylpyrazoles. - Google Patents

Abstract

The invention concerns insecticide compositions comprising: a) between 0.001 and 5 %, preferably between 0.05 and 1 % of a compound of the type 1phenyl pyrazole, in particular 1[2, 6Cl24CF3 phenyl] 3CN 4[SOCF3] 5NH2 pyrazole; and b) between 0.05 and 10 %, preferably between 0.1 and 5 % of one (or several) moisture retaining agent of the organic type; and c) between 40 and 99 %, preferably between 50 and 98 % (and more preferably between 70 and 97%) of vegetable flour. The invention also concerns a method for fighting insects using said composition, in particular against click beetles.

Description

PROCEDURE TO COMBAT THE INSECTS OF THE SOIL WITH FENIL-PIRAZOLES DESCRIPTION OF THE INVENTION The present invention has for its object new compositions intended to combat soil insects, in their various forms of development, and especially compositions useful for combating elaterids. The invention also relates to a method for combating using said compositions. Known, especially by patent applications EP-295117, O-87/3781, 93/6089 and 94/21606, phenyl-pyrazole-type insecticidal compounds usable for combating insects. Patent applications EP-295117 and 836386 also mention compositions containing 0.01% to 5% of such active materials. The elatéridos constitute a family of insects particularly harmful for certain crops, and more particularly for the crops of corn, beet, sunflower, potatoes and rapeseed. Its harmful nature is very marked, since the worms forms elaterids can remain in the ground, for very long periods that reach up to 5 years.

REF: 136311 Baits have been proposed for various kinds of insects, as well as formulas that are consumed by ingestion, but these formulas are not necessarily active for all kinds of insects, and there is a need to find insecticide forms or formulations particularly effective for more diverse applications, and in a special way to combat the elaterids. In addition, as regards insecticides applied on the soil or inside it, it is desirable to find conditions and formulations that allow good efficacy to be obtained at doses as low as possible. An object of the invention is to remedy, in whole or in part, these difficulties. Another object of the invention is to propose advantageous and effective compositions for combating non-gregarious insects. Another purpose of the invention is to propose advantageous and effective compositions for combating soil insects, especially elaterids, and more particularly elaterids in the state of worms. Another object of the invention is to provide compositions containing at least one insecticidal active substance of the phenyl-pyrazole type and conveniently applicable on the soil or in the interior thereof. ___. < t «t - * ..- > dfe_i. «. & __ »& __» _.._. _.to?-_ . - Y - . -. -J- ». *? It is also the purpose of the invention to propose insecticidal compositions which possess good performance, despite low doses of use. It has now been found that these objectives could be achieved, in whole or in part, by the compositions and the process for combating according to the invention, which are described in detail, below. It is specified that the percentages indicated in the present text are percentages in weight / weight, unless specifically indicated against. The subject of the present invention is therefore, first of all, insecticidal compositions containing: -a) between 0.001 and 5%, preferably between 0.05% and 1%, and even more advantageously, between 0.05 and 0. , 5% of a compound of formula (I): in which: Ri is a halogen atom, a CN group, a methyl group or a CH3CO R2 group is S (0) nR3; R3 is alkyl or haloalkyl; R4 represents a hydrogen or halogen atom; a radical NR5R6, S (0) mR7. C (0) R7 or C (0) 0-R, alkyl, haloalkyl 0R8 or a radical -N = C (R9) (R)? _; R5 and Re represent, independently, a hydrogen atom or an alkyl, haloalkyl, C (O) alkyl, S (0) eCF3 radical; R5 and R6 can together form a divalent alkylene radical which can be interrupted by one or two divalent heteroatoms, such as oxygen or sulfur; R7 represents an alkyl or haloalkyl radical; R8 represents an alkyl radical, haloalkyl or a hydrogen atom; Rg represents an alkyl radical or a hydrogen atom; Rio represents a phenyl or heteroaryl group optionally substituted by one or more halogen atoms or groups such as OH, -O-alkyl, -S-alkyl, cyano or alkyl; Rn and R12 represent, independently of one another, a hydrogen or halogen atom; R13 represents a halogen atom or a haloalkyl, haloalkoxy, S (0) qCF3 or SF5 group; _ »,» -_. < m, n, q, r represent, independently of one another, an integer equal to 0, 1 or 2; x represents a trivalent nitrogen atom or a C-R 2 radical, and the other three valences of the carbon atom form part of the aromatic ring; with the proviso that, when Rx is methyl, then R3 is haloalkyl, R4 is NH2, Rn is Cl, R3 is CF3 and X is N; -b) between 0.05 and 10%, preferably between 0, 1 and 5% of one (or several) moisture retaining agents, preferably, a moisture retaining agent, of organic nature; and -c) between 40 and 99%, preferably between 50 and 98% (and more preferably between 70 and 97%) of vegetable flour. The alkyl radicals of the definition of the formula (I) generally contain 1 to 6 carbon atoms.

The cycle formed by the divalent alkylene radical representing R5 and Rβ, as well as by the nitrogen atom to which R5 and Re. Are attached is generally a 5, 6 or 7-membered ring. The compound of formula (I) can be prepared according to one of the methods described in patent applications WO 87/3781, 93/6089, 94/21606, EP-295117 or also by another method contained in the general knowledge of the specialist skilled in the art. chemical synthesis. _fi ___ tt _____- This compound is also referred to in the present text by the term active material. Among the usable vegetable flours, we can mention the flours coming from the grinding of cereal grains such as wheat, barley, rye, triticale, oats, or also rice, sorghum, soybeans or corn, the preferred flour being the corn-based flour. . Similarly, a mixture of these vegetable flours can be considered suitable within the framework of the present invention. Among the agents, of an organic nature, moisture retainers, mention may be made of macromolecular hydrophilic derivatives of vegetable origin, and especially hydrophilic cellulose derivatives, and more particularly cellulose, but also one or more disintegration agents. It can be advantageous to use these compounds, in particular when they are used in flour granulates such as durum wheat flours. The disintegrating agents include: starch, sodium carboxymethyl starch, cellulose such as microcrystalline cellulose; modified celluloses such as sodium carboxymethyl cellulose; bentonite, aluminum and magnesium silicate; sodium polynaphthalene sulphonate, sodium dodecylbenzene sulfonate, sodium dioctyl sulfosucinate, lignin sulfonate; a sugar derivative such as lactose, fructose, sucrose, mannitol, dextrose; and a > _ £ _ »... -« - •, 'cross-linked derivative of polyvinylpyrrolidone. When a disintegrating agent is used, the composition according to the invention may contain 0.5 to 30% and, preferably, 1 to 20% by weight of dry substance, of the one or more agents mentioned. According to a variant of the composition according to the invention, the composition also contains 3 to 30%, preferably 4 to 20%, of sugars. The sugars are chosen especially among the mono- or poly-organosaccharides, in particular between sucrose, lactose, fructose, dextrose, glucose or also molasses or honey. The compositions object of the invention can also contain a preservative agent that prevents the degradation of flours, such as sodium benzoate, 1,2-benzoisot? Azolm-3-one, benzoic acid, para-hydroxybenzoic acid and its derivatives esters and alkaline or alkaline earth salts, especially the sodium salt, 2-phenylphenol and its alkali or alkaline earth salts, especially the sodium salt and para-nitrophenol. Other additives may also be included such as coloring agents or attractive agents for the harmful insects, or repellents for the birds or useful animals to be protected. Other formulation additives can be used as adhesive, binder, appetizing agents, Irifl ü ti A _: L _-_ L _._ ..S g binders, gelling agents, which produce swelling, non-stick and others. A preferred class of compounds of formula (I) is formed by compounds such that Ri is CN, and / or R3 is haloalkyl, R4 is NH2, Rn and Ri2 are, independently of each other, a halogen atom, and / or R13. is haloalkyl. According to a particularly advantageous variant of the invention, the compound of formula (I) used in the invention is 5-amino-3-cyano-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- [( trifluoromethyl) sulfinyl] -1H-pyrazole, which is referred to in the examples with the term "fipronil". The formulations according to the invention are generally in the form of granules. The size of the granulates is advantageously between 0.1 mm and 3 cm, preferably between 0.5 and 4 mm. These granules are advantageously insoluble in water (in the sense that they resist degradation by water). The compositions according to the invention can be prepared by simple mixing of the various constituents, preferably by cold or hot extrusion or compression, according to any known technique of granulation or preparation of pellets. To obtain such granulates, we will easily refer, for example, to the European patent application published under number RP-0575838 and / or to other techniques, for example extrusion, known to the person skilled in the art. The invention also relates to a process for the protection of crops against insects, especially elaterids, characterized in that an effective amount of an effective amount is applied on the soil or inside it (preferably inside it) in the area to be cultivated. composition in the form of granules of size between 0.2 mm and 2 cm, containing an active material chosen from the group consisting of the products of formula (I), imidacloprid, acetamiprid, nitenyram and thiamenthoxam. The products of formula (I) are preferred. The invention relates more particularly to a process for the protection of cereal crops, preferably maize or beet, sunflower, potatoes or rapeseed. The application of the formulations according to the invention takes place advantageously before sowing of said crop, or simultaneously with this sowing. The invention also relates to a method for combating insects, especially elaterids, characterized in that it is applied on the ground or inside it (preferably inside it) in which said insects are found or are likely to be found, an amount effective of one of the compositions according to the invention.

As effective amounts, amounts of composition are frequently used corresponding to a dose of compound of formula (I) comprised between 1 and 50 g / ha, preferably between 3 and 40 g / ha. A particular feature of the method for combating insects, according to the invention, consists in applying, on the ground or in its interior, a composition that provides a non-lethal dose by contact, but lethal by ingestion. In other words, in the particular case of elatéridos, the procedure consists of killing these elatéridos by application of a non-lethal dose by contact, but lethal by ingestion. A hypothesis of the good efficiency of the treatment method according to the invention, which allows the application doses of the compounds of formula (I) to be reduced significantly, is based on the fact that if the bait according to the invention has caused the death of an elatérido, this last one can serve as bait for other elatéridos that ingest, therefore, also a product (elatérido dead) that contains the insecticide. In the sense of the present text, the words insecticide and insect must be interpreted in their mainstream meaning and not in their strictly scientific (zoological) meaning. This is so so that for the term insect, any very small animal is understood, such as the arthropods (insects in the strict sense and zoological, arachnids, miriápodoso) and nematodes. As soil insects against which the invention is particularly effective, there may be mentioned for example: Coleoptera (wirewor s (Agriotes spp), false ire orms, white grabs) such as, for example: Agri otes linea tus (European elatérido, Elateridae ), Agri otes sordidus (European elatérido, Elateridae), Agriotes obscurus (European elatérido, Elateridae), Agri otes sputa tor (European elatérido, Elateridae), Athous spp. (Elateridae), Atomaria linearis (cryptophagidae), Mel olontha spp. (white worm, scarabacidae), Bothynoderes, Limoni us spp. (elatérido US), Melanotus spp. (Elatérido US) Diabroti ca spp. (cornrootworms, crysomelidae) Tanymecus pallidus (beet leaf weevil, curculionidae) Lepidoptera (Noctuelles) such as: Autographa spp., Mamestra spp, Agrotis spp. (Cutworms, gray worm), Euxoa spp. (Cutworms, gray worm), Spodoptera spp. (Spodoptera exigua, Spodoptera li t torlis).

L_t .__.__. X __-___ Diptera such as Tupula spp. Myriapoda (Myriapoda): -Dipl opoda = Miilipedes, -Centipede. Among the soil elatérides against which the invention is particularly effective, mention may be made of Agriotes spp., Athous spp., And Limonius spp. The granulates according to the invention are advantageously inserted into the soil at a depth of between 1 and 5 cm. The compositions according to the invention are particularly advantageous because they allow the use of lower doses of active compound than the known similar compositions. The following examples illustrate the invention, without constituting, in any way, a limitation thereof. In these examples, the compound of formula (I) used is fipronil.

Example 1: A surface area of 0.1 ha was planted with corn at a rate of approximately 8,000 seeds, untreated. This surface was divided into plots of 40 m2.

At the same time as the seed, 2 mm granules containing a composition consisting of: 0.25% fipronil, 93.5% corn flour, 2% cellulose were incorporated into the soil in the seed furrow. , 4% lactose, 0.2% para-nitrophenol, 0.05% blue pigment 15.3, The quantities of granules thus distributed ranged from 2.5 to 10 kg per hectare. Untreated parcels were conserved to serve as witnesses and verify the importance of the damage produced by the insects. In the same way, plots were treated with a commercial insecticide, reputed as effective, and called "Reference". Each modality was repeated four times. Approximately 20 days after sowing, corn plants that speak sprouted were counted. In the town of St Hilaire (30), 22 days after sowing, 19 plants per 10 meters of furrow were observed in the furrow of the 4 untreated plots. In the plots treated according to the invention with the dose of Fipronil of 6 g per hectare, 49 plants per 10 meters of furrow were observed.

With the dose of Fipronil of 12.5 g per hectare, 48 to 50.5 plants per 10 meters of furrow were observed. With the Fipronii dose of 25 g per hectare, 45.5 to 51.3 plants per 10 meters of furrow were observed. With the dose of Fipronil of 50 g per hectare, 49 plants per 10 meters of furrow were observed. To obtain the same result with a classic granulate (clay as support), it was necessary to provide 200 g of fipronil per hectare. The soil was scratched and scratched to capture and identify the insects responsible for the damage, and an important presence of elaterid larvae of the genus Agriotes, in particular Agriotes sordidus, was observed for the untreated control.

Example 2: Maize was planted at a rate of approximately 98,100 untreated grains, a surface area of 1 ha. This surface was divided into plots of 27 m2. At the same time as sowing, 2 mm granules containing a composition consisting of: 0.25 of fipronil, 93.5 of corn flour, 2% of cellulose, 4 were incorporated into the soil in the seed furrow. Lactose%, 0.2% para-nitrophenol, 0.05% blue pigment 15.3. The quantities of granules so spread varied from 2.5 to 10 kg per hectare. Untreated plots were kept to serve as witnesses and verify the importance of the damage caused by insects. In the same way, plots were treated with a commercial insecticide, reputed for its effectiveness, and called "reference". Each modality was repeated four times. Approximately 50 days after sowing, corn plants that speak sprouted were counted. In the town of Beaufort (62), 50 days after sowing, 30 plants per 10 meters of furrow were observed in the furrow of the four untreated plots. In the plots treated according to the invention, with the dose of Fipronil of 6 g per hectare, 40 plants per 10 meters of furrow were observed. With the dose of Fipronil of 12.5 g per hectare, 43 to 46 plants per 10 meters of furrow were observed. With the dose of Fipronil of 25 g per hectare, 45.5 to 50 plants per 10 meters of furrow were observed. With the dose of Fipronil of 50 g per hectare, 49.8 plants per 10 meters of furrow were observed.

To obtain the same result (52 plants per 10 meters of furrow) with a classic granulate (supported by clay) it was necessary to provide 200 g of Fipronil per hectare. The soil was excavated and scratched to capture and identify the insects responsible for the damage, and an important presence of elaterid larvae of the genus Agriotes, in particular Agriotes lineatus, was observed for the untreated control.

Example 3: Efficacy tests of the bait granules according to the invention, on a potato crop. At the same time as sowing, granulates according to the invention constituted by: 12.5 g / kg of fipronil (from a SC with 500 g / 1 of fipronil), 945 were incorporated into the soil in the sowing furrow. , 5 g / kg of flour a) of corn (granulated A) or b) of rice (granulated B), 40 g / kg of lactose, 2 g / kg of but-nitrophenol. The efficacy against Agriotes was compared (elatéridos) 90 days after the sowing of the two granulates A and B above, used at doses of 5 and 2.5 g of Fipronil per hectare, and of the same fipronil used by spray at doses of 50 and 25 g per hectare (from Regent (R) 800WG) (compound C). The following results were then observed, expressed in the number of perforations per 10 AN tubers: * untreated control This result clearly shows the good control of the elatérides obtained for the granulates according to the invention, which gave the same result as the Regent (R) 800WG, but with a dose reduced by a factor of 10.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers. . * _ * _-._. & ___.

Claims (11)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Insecticidal compositions characterized in that they contain: -a) between 0.001 and 5%, preferably between 0.05 and 0.5%, of a compound of formula (I): wherein: Ri is a halogen atom, a CN group, a methyl group or a CH3C0 group; R2 is S (0) nR3; R3 is alkyl or haloalkyl; R4 represents a hydrogen or halogen atom; a radical NR5R6. S (0) mR7, C (0) R7 or C (0) 0-R7, alkyl, haloalkyl or ORs or a radical -N = C (R9) (R)? _; R5 and Rβ represent, independently, a hydrogen atom or an alkyl, haloalkyl, C (0) alkyl, S (0) rCF3 or R5 and R can together form a divalent alkylene radical which may be interrupted by one or two divalent heteroatoms , such as oxygen or sulfur; R7 represents an alkyl or haloalkyl radical; R8 represents an alkyl radical, haloalkyl or a hydrogen atom; R9 represents an alkyl radical or a hydrogen atom; Rio represents a phenyl or heteroaryl group optionally substituted by one or more halogen atoms or groups such as OH, -O-alkyl, -S-alkyl, cyano or alkyl; Rii and 12 represent, independently of one another, a hydrogen or halogen atom; R13 represents a halogen atom or a haloalkyl, haloalkoxy, S (0) qCF3 or SF5 group; m, n, q, r represent, independently of one another, an integer equal to 0, 1 or 2; X represents a trivalent nitrogen atom or a C-Ri2 radical, the other three valences of the carbon atom forming part of the aromatic cycle; with the proviso that, when Ri is methyl, then R3 is haloalkyl, R4 is NH2, Rn is Cl, Ri3 is CF3 and X is N; -b) between 0.05 and 10%, preferably between 0.1 and 5% of one (or several) moisture retaining agents, preferably, a moisture retention agent, of organic nature; and -c) between 40 and 99%, preferably between 50 and 98% (and more preferably between 70 and 97%) of vegetable flour.
2. 2. Insecticidal compositions according to claim 1, characterized in that the flours come from the grinding of cereal grains such as wheat, barley, rye, triticale, oats, or also rice, sorghum, soybeans and corn.
3. 3. Insecticidal compositions according to one of claims 1 to 2, characterized in that the flour is corn flour. Insecticidal compositions according to one of claims 1 to 3, characterized in that among the moisture retaining agents, which are organic in nature, mention may be made of the macromolecular hydrophilic derivatives of vegetable origin, and especially the ____ t.lJ hydrophilic cellulose derivatives, and more particularly cellulose. Insecticidal compositions according to one of claims 1 to 4, characterized in that the composition also contains 3 to 30%, preferably 4 to 20%, of sugars. 6. Insecticidal compositions according to one of claims 1 to 4, characterized in that the sugars are chosen in particular from mono-, oligo-, or poly-organ-saccharides, especially between sucrose, lactose, fructose, dextrose, glucose or also molasses or honey Insecticidal compositions according to one of claims 1 to 6, characterized in that it also contains a preservative which prevents the degradation of the flours, chosen from sodium benzoate, 1,2-benzo-isothiazolin-3-one, benzoic acid , parahydroxybenzoic acid and its ester derivatives and alkali or alkaline earth salts, especially the sodium salt, 2-phenyl-phenol and its alkali or alkaline-earth salts, especially the sodium salt, and para-nitro-phenol. 8. Insecticidal compositions according to one of claims 1 to 7, characterized in that they contain other additives such as coloring agents or agents attractive to the insects that are harmful, or repulsive to the birds or animals useful or to be protected., and / or other formulating additives, such as adhesive, binder, appetizing agents, binders, gelling agents, swelling agents, anti-adherents and others. 9. Insecticidal compositions according to one of claims 1 to 8, characterized in that the compound of formula (I) is 5-amino-3-cyano-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- [(trifluoromethyl) snyl] -1H-pyrazole. 10. Insecticidal compositions according to one of claims 1 to 9, characterized in that the formulations according to the invention are in the form of granules, the size of these granules being advantageously between 0.1 mm and 3 cm, preferably between 0, 5 and 4 mm, and because these granulates are advantageously insoluble in water. 11. Process for combating insects, characterized in that an effective amount of a composition according to one of claims 1 to 10 is applied on or inside the soil (preferably inside the soil) of the area before being cultivated. in the form of granules of size between 0.2 mm and 2 cm. t < bta-J '' '? l ?? l _______ ÉIÍ _______ l-- 1